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DOE OSTI2022

Advanced Ceramic Membranes/Modules for Ultra Efficient Hydrogen (H2) Production/Carbon Dioxide (CO2) Capture for Coal-Based Polygeneration Plants: Fabrication, Testing, and CFD Modeling

Inorganic membrane-based systems are a promising technology for precombustion CO2 capture with simultaneous H2 production. State-of-the-art packages for high temperature and pressure service consist of multiple tube membrane bundles prepared in a "candle filter" configuration, in which the membrane tubes are open at one end and sealed at the other. This configuration is used for practical reasons, specifically the need to minimize problems due to thermal expansion mismatch between the ceramic tube bundle and the steel housing. However, the primary technical problem with the candle filter format for commercial-scale installations is the inability to purge the tube side (typically the permeate side), a feature that is crucial for high H2 recovery. In this study, the focus is to design and fabricate the first dual-end open full ceramic multiple tube membrane bundle that enables tube side (permeate) purge for gas separation applications. An additional key feature of this design is the simplified module layout, as the membrane bundles can be installed end-to-end with tube side (permeate) flow directly from one bundle to the next. This layout simplifies the membrane to housing seals and yields significant improvement in membrane packing density. Detailed focus areas in our studies include: (i) Materials development and preparation of the tube-to-tube sheet potting for the dual-ended bundle; (ii) the sealing and optimal module configuration design to minimize membrane stress upon module mounting; (iii) the demonstration, via the fabrication of CMS and Pd-alloy membranes supported on full-size, dual-ended ceramic support bundles, of the first example of a purgeable ceramic membrane and module; and (iv) development of a CFD model of the membrane module for calculation of feed flow distribution, and for use in scale-up, and capital cost estimating. The CFD model was validated using experimental data with the multi-tubular membrane system, employing He/N2 as a model gas mixture (surrogate for H2/CO2), and has been shown to be quite accurate. Employing the model, we are able to study the effects of operating pressure and temperature, feed and sweep gas flow rates, and the choice of membrane tube configuration on system performance.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2022

Advanced Ceramic Membranes/Modules for Ultra Efficient Hydrogen (H2) Production/Carbon Dioxide (CO2) Capture for Coal-Based Polygeneration Plants: Fabrication, Testing and CFD Modeling

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2017

Recovery Act: Pilot Integrated Cellulosic Biorefinery Operations to Fuel Ethanol

DOE EE002875 Technical Report Public Release. The objective was to leverage ICM’s pre-existing corn to ethanol pilot plant to build and to commission a fully functional pilot integrated cellulosic biorefinery. ICM’s Integrated Biorefinery (IBR) project was designed to achieve four major objectives. These primary goals were achieved during the performance period from December 2009 – August 2015. The design and construction phase took place from December 2009 until August 2011, with an increase in budget of nearly 4 million dollars. This increased cost was offset by operational changes, so the amount spent for the overall project increased by less than $500,000. There were three 1,000-hour performance test conducted, which produced cellulosic feedstock.

09 BIOMASS FUELS↗

DOE OSTI2026

An end-to-end workflow for executing a classically bootstrapped variational quantum algorithm on an academic quantum computer

Academic quantum computing platforms often face unique challenges in executing quantum workloads due to fragmented software environments and limited engineering support. Unlike commercial ecosystems, academic devices typically evolve without full-stack integration in mind, making it difficult to run complex applications—such as variational quantum algorithms (VQA)—reliably and efficiently. Issues such as incompatible software layers and lack of automated job management significantly increase the overhead of theory-experiment collaboration. To address these challenges, we develop a modular, end-to-end workflow that decouples application-layer code from low-level hardware control, automates circuit submission and result collection, and supports fine-grained circuit-level job scheduling and recovery. The architecture employs a dual-end application programming interface (API) design, enabling robust operation across unstable or resource-constrained hardware backends. For practical use, the framework is lightweight and user-friendly, allowing rapid prototyping of full-stack workflows using basic Python tools. We validate this workflow on a high-fidelity trapped-ion quantum computer by demonstrating a variational quantum eigensolver (VQE) experiment with a classically bootstrapped ansatz initialization technique. The system successfully executed over 60,000 circuits across multiple molecular test cases with minimal human intervention, highlighting the framework’s effectiveness in enabling reproducible, resilient quantum experimentation in academic settings.

Clifford↗

DOE OSTI2021

Machine learning based rate optimization under geologic uncertainty

We propose a novel approach for rate optimization during a waterflood under geologic uncertainty in reservoir properties such as permeability and porosity. The traditional approach typically involves several runs of the forward simulator. This may not scale well when the optimization is to be performed at the full field-level and over multiple geologic realizations. A machine-learning (ML) based approach which is quick and scalable for rate optimization over multiple geologic realizations is proposed instead. The training data for the model is generated by running the forward simulator with randomly assigned well rates using multiple geologic realizations. A reduced order representation of the permeability heterogeneity in each of the realizations is derived using a grid connectivity transformation (GCT). This step involves finding basis functions corresponding to the different modal frequencies of the grid connectivity represented by the grid Laplacian. The projection of the heterogeneous property field along these basis functions gives the basis coefficients that form the reduced order representation. Subsequently, for each training datapoint, streamlines are traced and the minimum time of flight (TOF) representing the tracer breakthrough time at each producer is recorded. The basis coefficients and well rates are fed to a machine learning model as input and the minimum TOF at the producers forms the output of the model. This trained model can then be used along with an optimizer for computing the optimal injection rates to maximize the injection sweep efficiency. This corresponds to minimizing the variance in the minimum TOF within each well group. Different architectures of neural network are tested using 5-fold cross validation to decide the best ML model to compute the streamline time of flight. The trained model is used to perform well rate optimization over multiple realizations of geology by using a risk tolerance penalty. The optimal well rates thus obtained are compared with two cases: a) equal well rates assigned to all injectors and producers and b) well rates obtained by optimizing over a single realization without considering the uncertainty in geology. The optimal well rates are seen to offer better oil recovery and sweep efficiency than both cases.

02 PETROLEUM↗

DOE OSTI2022

Study on Emulsification/Demulsification Behavior and Mechanism of Produced Liquid from Polymer Flooding on Alaska North Slope

Heavy oil reservoirs on Alaska North Slope (ANS) are unconsolidated and contain abundant clay minerals, where the first-ever field pilot is currently implemented to validate the use of polymer floods for heavy oil enhanced oil recovery (EOR). The polymer molecules and/or fine clay particles carried with the produced liquid could potentially affect the oil/water separation, which is one of the major concerns for field operators. This dissertation aims to investigate the emulsification behavior of produced liquid, understand the emulsifying mechanism, and seek an adaptive and cost-effective method to treat the produced liquid from polymer flooding. Emulsions were prepared by mechanically mixing the actual heavy oil and the produced water from the pilot site, of which the stability was investigated by bottle test method or multiple light scattering method. Drop size distribution and interfacial properties were measured via microscope and pendant drop technique to probe the stability mechanism further. Results showed that oil-continuous or water-continuous emulsion could be generated depending on the water cut, clay types, clay concentration, and polymer concentration. In the crude oil/water system, the increasing water cut triggered the phase inversion of oil-continuous emulsion to water-continuous emulsion, resulting in faster separation and lower emulsion stability. Whereas, clay particles, no matter added to the oil or water phase, resulted in an unfavorable phase inversion from the loose water-continuous emulsion to the tight oil-continuous emulsion as clay concentration increased. For all four types of clay except Ca-montmorillonite, clay particles added to water led to an earlier phase inversion and higher emulsion stability than that added to the oil. The dual function of polymer on emulsion stability was observed. On the one hand, both sheared and unsheared polymer tended to convert the oil-continuous emulsion formed in either crude oil/water system or complex crude oil/water/clay particle system to the water-continuous emulsion, acting as a weak demulsifier to accelerate the oil/water separation. On the other hand, the addition of polymer to the water-continuous emulsion could result in enhanced emulsion stability, which is primarily attributed to the increased viscosity of the continuous phase and the decreased drop size of the dispersed oil phase. Particularly, the sheared polymer had a weaker ability to stabilize the o/w emulsion than the unsheared polymer due to the lower viscosity of the sheared polymer solution resulting from the breakdown of the polymer macromolecules. As for the chemical demulsification tests, the performance of demulsifiers showed a complex dependency upon the water cut, the shearing intensity, demulsifier type and dosage, and the polymer concentration. A compound emulsion breaker, E12+E18, exhibited the most satisfactory demulsification performance despite the varied test conditions. For severe water-continuous emulsions that might require a multi-fold dosage of demulsifier, a less expensive electrolyte, KCl, was proposed to be used in combination with demulsifier E12+E18 to improve the demulsification performance. In the proposed demulsifier formula, the effectiveness of the commercial demulsifier relied on its destructive effect on the interfacial film, while the efficacy of KCl was mainly dependent on its viscosity reduction effect on the continuous phase. This dissertation illustrates that intermediate layer elimination and water clarification are the major challenges for produced liquid treatment from polymer flooding. It also provides practical and theoretical guidance in advance for the demulsification strategy of the produced liquid from the ongoing first-ever polymer flooding pilot on ANS.

Chang, Hongli↗

DOE OSTI2023

Stacked Greenfield and Brownfield ROZ Fairways in the Illinois Basin Geo-Laboratory: Co-Optimization of EOR and Associated CO 2 Storage

Residual oil zones (ROZs) are economically viable targets for carbon dioxide enhanced oil recovery (CO 2 -EOR); thick, carbonate ROZs in the San Andres Formation in the Wasson Field of the Permian Basin are an example. Incremental oil produced from CO 2 -EOR can be carbon negative via associated storage of injected CO 2 . Given the regional extent of ROZ fairways and generally higher net utilization of CO 2 (compared to conventional CO 2 -EOR), ROZs provide the opportunity for significant carbon neutral to carbon negative oil production with associated CO 2 storage, and therefore should be a priority target for exploration. However, ROZs have not been widely recognized or identified due to poor or no conventional oil production. Hence, in places like the Illinois Basin (ILB), exploratory analyses are required to recognize the existence of an ROZ. As part of this study, four formations were selected for detailed regional characterization and analysis: Carper Sandstone (part of the Borden Siltstone), Tar Springs Sandstone, Cypress Sandstone, and Middle Devonian (Geneva Dolomite and associated Dutch Creek Sandstone). The four formations underwent regional geological characterization to develop a regional geologic framework for the ROZs and their overlying seals. Findings of this study are supported by data from two field laboratory sites, one with stacked greenfield ROZs and the other with a stacked complex that includes a brownfield ROZ and depleted conventional reservoirs. The field laboratory sites were used to collect data and conduct tests to validate ROZ detection methodologies and identify economic field-deployable strategies to co-optimize CO 2 -EOR and associated storage in stacked ROZs. Findings from these field sites were extrapolated to characterize the basin-wide stacked ROZ fairway resource.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2018

Downhole Microseismic Mapping of More Than 400 Fracturing Stages on a Multiwell Pad at the Hydraulic Fracturing Test Site (HFTS): Discussion of Operational Challenges and Analytic Results

The United States Department of Energy co-funded a joint industry project (JIP) in the Midland basin of Texas. The project was conducted in the Wolfcamp formation to better understand the relationships among horizontal lateral placement, production interference between laterals, effectiveness of completion sequences, and hydraulic fracture geometry in unconventional reservoirs. Downhole microseismic data was acquired from more than 400 fracturing stages during the completion project to better understand the generated hydraulic fracture geometries. Eleven horizontal wells were drilled in the upper Wolfcamp (UW) and middle Wolfcamp (MW) formation in the Permian Basin. The 10,000-ft laterals were drilled in a chevron pattern to help improve inter-well fracture communication and maximize hydrocarbon recovery. The completions sequences were planned to restrain fracture height growth upward into a lower-pressure zone using a combination of zipper fracturing and simultaneous fracturing operations. Downhole microseismic monitoring was used to record more than 95% of the planned fracture stages. Downhole tiltmeters were also used to validate upward fracture height growth. Multiple geophone arrays, both vertical and horizontal, were used during this completion; this paper discusses coordination between maintaining completion efficiency and obtaining microseismic data. Additionally, this paper highlights the completion challenges associated with collecting diagnostic data along with results and findings.

Stegent, Neil A.↗

DOE OSTI2016

Utilizing geothermal heat for hydrothermal liquefaction of algae

The distribution of utilizable geothermal reservoirs in the US is concentrated in areas of low population density. In order to increase the scale of geothermal operations, we proposed to develop a modular biofuel production facility that directly uses geothermal heat. By transforming geothermal heat to chemical potential energy (rather than electricity), the scale of existing or new geothermal operations can be increased and distributed to areas of higher population density. Simultaneously, the economics of producing biocrude oil is improved significantly where geothermal heat is used, instead of natural gas-fired systems for providing heat and power. In the Phase I project, we demonstrated that it was economically feasible to sustainably produce a biofuel by integrating geothermal heat. It was found that, for the best case scenario at a scale of 10T(biomass)/hr, it was possible to produce a biofuel for $0.26/L, as compared to crude oil at $0.3/L (current selling price). Ultimately this demonstrates that this technology can be economically sustainable when integrated with geothermal heat. We also demonstrated that the addition of modular biofuel-production technologies can be more profitable for a geothermal plant operator. For 1000kg/day scale, it was found that it could be 2.5 times more profitable for a geothermal plant operator to sell bio-oil rather than electricity (with a waste source within 20 miles of the processing facility). Furthermore, as the design of the proposed technology recycles significant heat, requiring between 5% and 20% of the total heat load of the biofuel process to be supplied by the geothermal plant, it is feasible for an operator to initially implement the technology at small scale (i.e. less than 100gal/day) with the plans of scaling up operations in the future. Implementing the technology incrementally may minimize initial the investment and financial risk for the operator. Finally, in the Phase I project, we built and tested a hydrothermal system developed at ARI. We tested three different feedstock types, pure algae feed, algae mixed with manure, and algae with in-situ catalysts (molybdenum trioxide), over a range of temperatures and residence times. In terms of oil products, our results (yield, process times and elemental balance) were similar to what was obtained at PNNL. As such our experiments matched well with the techno-economic design (mass throughput specifications), and will thus well inform the Phase II process design. The experimental data obtained on the hydrothermal treatment of algae indicated that the highest recovery of oil occurred at 250°C. This shows that HTL can be carried out 100°C lower than what is currently considered ‘state of the art’, and thus save significant energy savings. Further, it was found that oil-recovered fractions had lower amounts of nitrogen at lower temperatures, indicating that oil produced at 250°C is of higher quality than if we were to produce fuel at 350°C.

09 BIOMASS FUELS↗

DOE OSTI2019

Self-healing, re-adhering, and carbon-steel corrosion mitigating properties of fly ash-containing calcium aluminum phosphate cement composite at 300 °C hydrothermal temperature

This study assesses here the ability of calcium aluminate phosphate (CAP)/fly ash F (FAF) blend composite to self-heal at early age; to re-adhere to the casing surfaces after debonding and to protect carbon steel (CS) against brine-caused corrosion before and after the re-adherence. The composite was damaged after autoclaving for 24 h at 300 °C and then exposed to the same conditions for 5 more days for the self-healing and re-adhering processes. The ability of the blend to self-heal and re-adhere to CS was evaluated 1) by measurements of the recovery of compressive and bond strengths and Young's modulus; 2) by performing the 3-dimensional micro-image analysis of sealed cracks; 3) by phase identification in composite matrix and in the cracks after the healing; 4) by measurements of CS corrosion impediment by the re-adhered composite after 300°C-5-day restoration period. After the healing, the two factors, sealing effect of cracks by reaction products and change in phase composition of cement matrix, essentially governed the recovery of the original mechanical strength. For the former, analcime phase derived from pozzolanic FAF autogenous healing aid played the major role in sealing the cracks, while the well-formed hydroxyapatite phase contributed to the latter factor. The lap-shear bond with the strength of 1.11 MPa at CS plate/composite adhesive/CS plate joint failed cohesively, showing higher bond strength than strength of the composite matrix. The rebonded composite-CS plates developed a 0.37 MPa bond strength after the 5-day restoration period. The results of electrochemical polarization corrosion tests revealed that the re-adhered composite covering CS plate significantly inhibited the brine-caused corrosion of CS, leading to 0.011 mm/year corrosion rate, corresponding to 50% reduction compared with that of before re-adhering. There were two factors governing such corrosion mitigation: enhanced adhesive contact of composite with CS and increased coverage by the re-adhering composite.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Decontamination of urban surfaces contaminated with radioactive materials and consequent onsite recycling of the waste water

Enhancing rapid remediation strategies is paramount for recovery after a large-scale nuclear contamination event in an urban environment. Some current strategies recommend use of readily available equipment, materials, and facilities to expedite recovery. For example, applying pressurized water to contaminated surfaces may effectively remove radioactive contamination. In this study, a commercial power washer removes soluble forms of 152 Eu 3 + , 85 Sr 2 + , and 137 Cs + contamination from common porous building materials, and computer simulations characterize the recycling of the resultant contaminated wash water. Pressure washing the porous building materials under spray conditions typical with do-it-yourself units improved decontamination factors (DFs) for 152 Eu compared to low-pressure application of tap water (majority of two-tailed t-test p-values < 0.1), but pressure did not improve DFs for 137 Cs or 85 Sr. For both pressurized and low-pressure applications, adding potassium ions (K + ) to promote ion exchange reactions produced significantly higher DFs for tested radionuclides on asphalt, brick, and concrete. The resultant contaminated wash water can be processed through self-prepared chemical filtration beds of clay and sand. Modeled in a prior study, the beds yielded linear trends (R 2 > 0.98) in sensitivity analyses between most bed configuration variables and bed performance variables, permitting flexible ad-hoc bed design. The experimental and simulation results led to estimates of the remediation rate and waste generated after cleaning 250 m 2 of cesium-contaminated concrete from the combined deployment of a power washer and two different mobile treatment beds. Furthermore, the first treatment bed was designed to reduce treatment time and processed 1900 L of wash solution in 70 min using 880 kg of clay/sand infill material. Designed to reduce the solid waste generated, the second bed processed the same solution volume in 1040 min (17 h) using 170 kg of clay/sand infill material. The results of this analysis warrant further investigation of power washing with recycled salt solution as an effective rapid decontamination method with manageable waste.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Accounting for the effect of dislocation climb-mediated flow on the anisotropy and texture evolution of Mg alloy, AZ31B

The current study explores the role that dislocation climb has in mediating plasticity a Mg alloy at moderately elevated temperatures. Interrupted tensile tests were performed on samples of Mg alloy, AZ31B, sheet in the O temper condition over a range of strain rates (10 -5 to 10 -1 s -1 ) and temperatures (20–350°C) along the rolling and transverse directions. Experimental measurements of the resulting strain anisotropy and texture evolution were used as constraints during a parametric study employing a new crystal plasticity model (VPSC-CLIMB), which explicitly accounts for the kinematics of dislocation climb. The results reveal that the climb of basal (a) dislocations is not only important for dislocation recovery, but also demonstrate that climb accommodates a significant fraction of the strain in conditions where a power-law creep-type constitutive response prevails. This work does not discredit the notion that non-basal slip of (a) and (c+a) dislocations is important over a wide range of temperatures and strain rates. However, it demonstrates that the activation of dislocation climb as the mechanistic change within the power law regime provides an explanation for a wide range of observations, including the simultaneous reduction in strain anisotropy, slowed texture evolution, and rapid increase in strain rate sensitivity. Finally, it is hypothesized that these conclusions may even apply to cases in which grain boundary sliding and/or dynamic recrystallization are observed.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Endpoint Evaluation for 200-PW-1 Operable Unit Soil Vapor Extraction, Hanford Site, Washington - 16478

On the Central Plateau of the Hanford Site in semi-arid southeast Washington State, the 216-Z-9 Trench, 216-Z-1A Tile Field, and 216-Z-18 Crib were used from 1955 to 1973 for soil column disposal of liquid wastes containing carbon tetrachloride. The geological setting underneath these disposal areas consists of an approximately 70 m thick vadose zone with a nominally 5 m thick low-permeability layer at a depth of 30 m. Infiltration of the liquid waste through the vadose zone to the groundwater was driven by the liquid volume introduced during disposal. Carbon tetrachloride readily volatilises in the vadose zone, making soil vapor extraction (SVE) the preferred remediation technology. Between 1992 and 2012, SVE recovered 80,107 kg of carbon tetrachloride from the vadose zone below the three waste sites. Of this total recovery, 93 percent was removed during the first 5 years of operations. The last 7 percent was recovered in the last 16 years of operation. In 2011, a final cleanup level of 100 ppmv for carbon tetrachloride in soil vapor was established in the record of decision for the 200-PW-1 Operable Unit, which includes the three carbon tetrachloride waste sites. The final cleanup decision specified that soil vapor concentrations and the cleanup level would be further refined and assessed in the future to ensure groundwater protection. A subsequent treatability test was conducted and the results were used to further refine the definition of vadose zone source conditions that are protective of groundwater. Based on this treatability test, predictions indicate that current and future vadose zone conditions will meet groundwater protection objectives. SVE operations were not performed in 2013, 2014, and 2015, and soil vapor concentrations in all SVE wells (and all but two monitoring probes installed using direct-push technology) remained below the 100 ppmv cleanup level during this time. SVE endpoint guidance was prepared in 2013 as a joint effort between Pacific Northwest National Laboratory, U.S. Army Corps of Engineers, and U.S. Environmental Protection Agency. This SVE guidance was used to develop a path forward for the 200-PW-1 Operable Unit SVE remedy. The guidance asks the following questions: 1. Are data collected to date adequate to support a well-defined conceptual site model? 2. Have remediation goals (cleanup levels) been defined? 3. Are environmental pathways and risk understood well enough to support site closeout? 4. Will remaining contamination in the vadose zone cause groundwater cleanup levels to be exceeded? If the answer to the first three questions is 'Yes', and the answer to the fourth question is 'No', then the site is ready for closure. At this time, the site has compiled appropriate information to answer these questions to support a remedy decision to terminate SVE operations. The U.S. Environmental Protection Agency recently provided concurrence that termination of SVE operations within the 200-PW-1 Operable Unit is appropriate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Direct LiT Electrolysis in a Metallic Fusion Blanket

A process that simplifies the extraction of tritium from molten lithium-based breeding blankets was developed. The process is based on the direct electrolysis of lithium tritide using a ceramic Li ion conductor that replaces the molten salt extraction step. Extraction of tritium in the form of lithium tritide in the blankets/targets of fusion/fission reactors is critical in order to maintain low concentrations. This is needed to decrease the potential tritium permeation to the surroundings and large releases from unforeseen accident scenarios. Extraction is complicated due to required low tritium concentration limits and because of the high affinity of tritium for the blanket. This work identified, developed and tested the use of ceramic lithium ion conductors capable of recovering hydrogen and deuterium through an electrolysis step at high temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Recovery of Rare Earth Elements from Bioleachates by Precipitation

Rare earth elements are essential components in electronic devices, however because of the limited imports and mining capabilities in the US, recycling these rare earths is crucial. Common practices used to recover REEs including hydrometallurgy and pyrometallurgy are harmful to the environment. Bioleaching, a form of biohydrometallurgy, is an emerging process that uses organic acids synthesized by microorganisms and can leach REEs at comparable efficiencies to less environmentally conscious processes. Once the REEs are leached by the bio-lixiviant produced by microorganisms, the REEs are suspended in the solution and need to precipitate out in order to be harvested for reuse. Common chemicals used for rare earth precipitation in hydrometallurgy processes include sodium sulfate and oxalic acid. These two reagents were tested at varying stoichiometric excess concentrations in bio-leachate derived from smart phone speaker magnets and bio-lixiviant. Following the precipitation reactions, it was observed that the oxalic acid reaction precipitated an abundance of iron (II) oxalate, an REE contaminate. This is most likely due to the bio-leachate having a higher pH compared to the hydrometallurgical leachates. Therefore, it was determined that sodium sulfate is a better candidate for REE precipitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Design and evaluation of a dilute flow particle-to-air heat exchanger for energy storage applications

The use of inert and redox-active particles for high-temperature energy storage requires the development of components that can efficiently transfer energy to high-pressure working fluids like supercritical carbon dioxide (sCO 2 ). Dilute flow reactors can enable high working fluid outlet temperatures and minimal parasitic losses compared to moving packed bed and fluidized bed reactors. This research uses both computational and experimental methods to explore the design trade-offs and practical challenges of a novel component for transferring energy from dilute flows of hot, reduced metal oxide (MO x ) particles to sCO 2 in tubes. A discretized thermal resistance network model, which accounts for particle hydrodynamics, multi-mode heat transfer, and reaction equilibrium, guides the design of a prototype device. This device is experimentally tested with a surrogate heat transfer fluids and inert particle temperatures up to 400°C and a heat duty exceeding 1 kW. The data are used to validate the thermal hydraulic sub-models, allowing for the simulation of reacting particle scenarios. Under nominal design conditions, the flow rate of reactive particles is predicted to be 30% lower than that of inert particles for the same energy recovered, with over 70% of the stored particle energy transferred to the sCO 2 . Furthermore, these findings can inform the design of more efficient energy recovery reactors for particle-based systems and can be integrated into system-level concentrated solar power models with thermal storage to optimize operating conditions.

14 SOLAR ENERGY↗

DOE OSTI2016

Development of HSPA1A promoter-driven luciferase reporter gene assays in human cells for assessing the oxidative damage induced by silver nanoparticles

The exponential increase in the total number of engineered nanoparticles in consumer products requires novel tools for rapid and cost-effective toxicology screening. In order to assess the oxidative damage induced by nanoparticles, toxicity test systems based on a human HSPA1A promoter-driven luciferase reporter in HepG2, LO2, A549, and HBE cells were established. After treated with heat shock and a group of silver nanoparticles (AgNPs) with different primary particle sizes, the cell viability, oxidative damage, and luciferase activity were determined. The time-dependent Ag{sup +} ions release from AgNPs in cell medium was also evaluated. Our results showed that heat shock produced a strong time-dependent induction of relative luciferase activity in the four luciferase reporter cells. Surprisingly, at 4 h of recovery, the relative luciferase activity was > 98 × the control level in HepG2-luciferase cells. Exposure to different sizes of AgNPs resulted in activation of the HSPA1A promoter in a dose-dependent manner, even at low cytotoxic or non-cytotoxic doses. The smaller (5 nm) AgNPs were more potent in luciferase induction than the larger (50 and 75 nm) AgNPs. These results were generally in accordance with the oxidative damage indicated by malondialdehyde concentration, reactive oxygen species induction and glutathione depletion, and Ag{sup +} ions release in cell medium. Compared with the other three luciferase reporter cells, the luciferase signal in HepG2-luciferase cells is obviously more sensitive and stable. We conclude that the luciferase reporter cells, especially the HepG2-luciferase cells, could provide a valuable tool for rapid screening of the oxidative damage induced by AgNPs. - Highlights: • We established the stable HSPA1A promoter-driven luciferase reporter cells. • Silver nanoparticles induced dose-dependent increases in luciferase activity. • HSPA1A promoter activity is a sensitive and responsive indicator of oxidative stress. • HepG2-luciferase cells can be used to assess the toxicity of silver nanoparticles.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2016

Inhibitory Effect of Furanic and Phenolic Compounds on Exoelectrogenesis in a Microbial Electrolysis Cell Bioanode

Furanic and phenolic compounds are 20 lignocellulose-derived compounds known to inhibit to H2- and ethanol- producing microorganisms in dark fermentation. Bioelectrochemical conversion of furanic and phenolic compounds to electricity or H2 has recently been demonstrated as a productive method to use these compounds. However, potential inhibitory effect of furanic and phenolic compounds on exoelectrogenesis in bioelectrochemical systems is not well understood. This study systematically investigated the inhibitory effect of furfural (FF), 5-hydroxymethylfurfural (HMF), syringic acid (SA), vanillic acid (VA), and 4-hydroxybenzoic acid (HBA) on exoelectrogenesis in the bioanode of a microbial electrolysis cell. A mixture of these five compounds at an increasing initial total concentration from 0.8 to 8.0 g/L resulted in current decrease up to 91%. The observed inhibition primarily affected exoelectrogenesis, instead of non-exoelectrogenic biotransformation pathways (e.g., fermentation) of the five compounds. Furthermore, the parent compounds at a high concentration, as opposed to their biotransformation products, were responsible for the observed inhibition. Tests with individual compounds show that all five parent compounds contributed to the observed inhibition by the mixture. The IC50 (concentration resulting in 50% current decrease) was estimated as 2.7 g/L for FF, 3.0 g/L for HMF, 1.9 g/L for SA, 2.1 g/L for VA and 2.0 g/L for HBA. Nevertheless, these compounds below their non-inhibitory concentrations jointly resulted in significant inhibition as a mixture. Catechol and phenol, which were persistent biotransformation products of the mixture, inhibited exoelectrogens at high concentrations, but to a lesser extent than the parent compounds. Recovery of exoelectrogenesis from inhibition by all compounds was observed, except for catechol, which resulted in irreversible inhibition. The reversibility of inhibition, as well as the observed difference in recovery rates, suggest different modes of exoelectrogenesis inhibition, related to the hydrophobicity of the inhibiting compounds.

60 APPLIED LIFE SCIENCES↗